DE1694306B2 - STORAGE FORM AND SEALING COMPOUNDS ON THE BASIS OF BLOCK MIXED POLYMERS OF SILICONE - Google Patents

Description

R '

have, wherein R 'and R "have those in claim 1 have given meaning.

, 5. Molding composition according to claim 1 or 2, characterized characterized in that the polycarbonate blocks of the copolymer with polydiorganosiloxane blocks, the terminal

or

Il

-C ₃ H ₆ NHCO
O

-C ₃ H ₆ OCNH

to the copolymer via carbon-Silicivyn bonds are linked.

R 'O

I Il

OSiR "CO units

I.
R '

The invention relates to one at a content of < 100 ppm water storable molding or sealing compound based on block copolymers, which over C-Si bonds monovalent organosilyl radicals of the formula

have, are chemically linked, where R 'and R "have the meaning given in claim 1.

6. Molding composition according to claim 1 or 2, characterized in that the polycarbonate blocks of the Copolymers with diorganopolysiloxane blocks are chemically linked, the terminal

R 'O

- OSiR "OCNHR" HNCO units

R '

have, wherein R, R 'and R' "are those in claim 1 have given meaning.

7. Molding composition according to claim 1 or 2, characterized in that the copolymer is monovalent Organosilyl radicals of the formula

Ii

(H ₃ CCO) ₃ -Si (CH ₃ ).

having, wherein the organosilyl radicals by divalent organic residues

Y ₃ -JSiR.

where Y is a hydrolyzable radical, R a monovalent one free of aliphatically unsaturated bonds Hydrocarbon radical or a halogenated monovalent hydrocarbon radical and a has a value of 0, 1 or 2 means, contained in bound form, which hardens on contact with atmospheric moisture and which, in addition to fillers, optionally solvents, also contains catalysts, which are characterized in that is that the copolymers are made up of chemically linked blocks of

(A) 1 to 95 percent by weight organopolysiloxane, which in turn consists of chemically linked diorganosiloxy units the formula

RjSiO

is constructed, as well

(B) 5 to 99 percent by weight of a reaction product from the reaction of a dihydroxy compound of formula

-C ₃ H ₆ OCO-

HO-Z-OH

with a dihalide of carbonic acid or a diaryl carbonate, where R 'is a monovalent Hydrocarbon radical, a halogenated monovalent hydrocarbon radical or a cyanoalkyl radical and Z means the same as R "or R" WR ", where again R" is a divalent hydrocarbon radical or a halogenated divalent hydrocarbon residue and W a bivalent

-C ₃ H ₆

R '"

- C-- rest
R '"

a divalent cycloaliphatic radical, a divalent oxyarylenoxy radical, a sulfonyl, sulfi-

nyl, oxy or thio radical and R '"is hydrogen or one R-residue means

To the organopolysiloxane-polycarbonate block copolymers curable at ordinary temperatures include those in which theorganizilylrest of Formula (1) is in the end position

These copolymers cannot be claimed here Way can be produced by carrying out an additive reaction between a silicon-hydrogen bond containing compound of the formula

produced here in a manner not claimed by ikß a mixture of (C) from the Dihydroxyverbhiduag according to formula (3), (D) an organopolysiloxane of the formula

G-

R '

SiO

R '

R "

SiG

R '

Y ₃ - _e SiH

(4)

and (E) an aliphatically unsaturated monohydroxy compound the formula

and an organopolysiloxane-polycarbonate block copolymer, the terminal olefinically unsaturated group of the form]

; "- CRQ

(5)

CR: "-C -R" OH

where R '. R ", b, d and the grouping

where b is 1 or 2, d is 0 or 1 and the grouping

Ri "

cr; "-c

CR ^ "- C have the aforementioned meaning, and G the

_ symbolizes the following radicals: Part of an unsaturated aliphatic radical, such as a 30

olefinic, acetylenic or unsaturated cycloaliphatic Is remainder and Q is a divalent, non-polar linking grouping, such as

- O
H O
Η O
π - O- Il
-OCO Il
'NCO - O
Il R '"O
I Il O
Μ Il
-CO I Il
-N —CO- Il
'CO- Il
- NHCO - Ό - O
π OCNHR ' O
π Il
- OCR ' O -COR '

35

40

45 or

- SCR ^ 'CO -

means, where Y, R, R "and R '" have the aforementioned meaning.

Block copolymers with terminal aliphatically unsaturated ones Residues of the formula (5) which are linked to the copolymer via carbonate bonds are shown in

- OZOH -ROH

o o

Il 11

- R'OCOZOH - R-COH

Il

-R-COZOH

O
- R "NHCOZOH

O O

Il Il

- R "OCNHR" HNCOZOH

where Z and R ″ have the abovementioned meaning and η denotes an integer from 1, including 500, to exposure to phosgene.

In formula (6), where G is the R "Q bond between the organopolysiloxane blocks and the polycarbonate blocks, R means "before preferably an alkylene radical, a divalent cycloalkane or alkylenearylene radical or their halo gender derivatives, for example ethylene, propylene-butylene, cyclobutylene, cyclopentylene, ethylene pheny len or propylene chlorophenylene radical.

For the purpose of defining block copolymerization by the percentage by weight of organopolysiloxane blocks in the copolymer, based on the total weight of the copolymer, the weight of the organopolysiloxane blocks is given in the measure of the chemically linked organosiloxane units, albeit OZOH residues ai before the action of phosgene

the organopolysiloxane can be linked. Copolymers which have R "Q bonds between the organopolysiloxane blocks and the polycarbonate blocks have the weight of the R" Q bonds plus the weight of the organopolysiloxane blocks. The weight of the terminal R "Q radicals of the formula ( ^c ) and the attached radicals according to the formula (1) are included in the weight of the polycarbonate blocks.

The organopolysiloxanes of the formula (S), the terminal ones Have OZOH radicals can in a manner not claimed here by reacting a dihydroxy compound of the formula (3) with a halogen-endblocked organopolysiloxane of the formula

R 'IR X - + - SiO-f- SiX ι Nl

; i ι

i R 'L R'

according to the process described in US Pat. No. Jl 89 tb2. In the above formula (8), X represents a halogen atom.

The dihydroxy compounds of the formula (3) which can preferably be used are bisphenols of the formula

HO

R "

(9)

in which R '"has the meaning given above, E = X or an alkyl radical and / an integer from 0 to 4 is.

The organopolysiloxanes of the formula (6). the terminal organohydroxy radicals of the formula

HOR "

R '
SiO

R '

R 'SiROH

R '

(10)

45

have, in which R ', R "and π have the meaning given above , form carbonate bonds when they are treated with phosgene in the presence of dihydroxy compounds of the formula (3). The organopolysi] oxanes of the formula (10) can by equilibrating Cydopolysfloxanes of the formula

R '

-SiO-

R '

can the organopolysiloxanes of the formula (10) by addition of a compound of the formula

H - 4-

R '

SiO

R '

R '

SiH

R '

into an aliphatically unsaturated hydroxy compound have been manufactured, with all dimensions having the above meaning. Furthermore, a direct equilibrium can be Bring a low molecular weight addition product such as the disiloxane of the formula (10) and an above specified cyclopolysiloxane, are used.

In addition to the organopolysiloxanes of the formula (10) which contain terminal organohydroxy radicals, zui Production of copolymers with carbonate bonds Or ganopolysiloxane of the formula (6) are used terminal ester bonds of the formula

Il

HOZOCR

R '

SiO
R '

R 'O

1 Il

SiR "COZOH

R '

have, where all dimensions have the above meaning. Terminal ester bonds are used in the Oigen organopolysiloxanes preferably by Um setting an organopolysiloxanoic acid halide with a hydroxy compound of the formula (3) in the presence an acid acceptor such as pyridine. Organo polysüoxansäurehalogenide can by equilibrium tion of mixtures of cyclopolysiloxanes unc 1,3-bis (carboxyalkyl) tetraorganosiloxanes

1.3-bis (carboxyaryl) tetraorganosiloxanes and Um convert the resulting carboxy-endblocked Orga nopolysiloxane into the organopolysiloxanoic acid halogen nid, as stated above, be preserved. A halogen longitudinal process is in US Patent 31 11 85! described.

Further examples of organopolysiloxanes encompassed before formula (6) are organopolysiloxane polymers with terminal urethane bonds of the formula

YOR "

R '

SiO

R '

R '

SiR "OY '

R '

where Y 'e.g. R following grouping O

-CNH

in which R 'has the above meaning and means my whole number from 3 to 20, with ^ -Diorgano-l-oxa - ^ - sflacycloaTkanen, like 2 £ -Dimethy! -l-oxa-2-silacydohexane or 2 ^ -Diphenyl-1-oxa-2-silacyclohexane have been. These silacydoalkanes are in the U.S. Patent 3,083,219. aside from that

O = CO

OH

R "'

can be.

As shown above, the organopolysi] oxane-polycarbonate copolymers with terminal al

609530/41

phatically unsaturated radicals of the formula (5), which have Carbonate bonds are linked to the copolymer by the action of phosgene on a mixture • us of a dihydroxy compound of the formula (3), an organopolysiloxane of the formula (6) and an olefinic one unsaturated hydroxy compound of the formula (7) have been prepared. Olefinically unsaturated block copolymers, which have terminal olefinically unsaturated radicals of the formula (5) can by a Multi-stage process be produced. A mixture of a dihydroxy compound of formula (3) and an organopolysiloxane of the formula (6) may have been treated with phosgene. The obtained copolymer may then have been treated with an aliphatically unsaturated compound of the formula (7) or the phosgenated mixture can, after hydrolysis, be treated with an aliphatically unsaturated isocyanate of which a polyisocyanate in combination with an aliphatically unsaturated hydroxy compound of the formula (7).

Another for the production of organopolysiloxane-polycarbonate block copolymers a suitable process is transesterification with diaryl carbonate and dihydroxy compounds of the formula (3). This method is on pages 44 to 51 of the book Chemistry and Physics of Polycarbonates, by Herman Schnell, Interscience Verlag, John Wiley and Sons, New York (1964). Another method that used is based on the direct action of phosgene on a mixture of EH hydroxy compounds of the formula (3) and organopolysiloxane of the formula (6) with terminal carboxy radicals.

Isocyanates that may have been used to remove terminal olefinic unsaturation in the copolymer instead of the monohydroxy compound of formula (6) are olefinically unsaturated ones Isocyanates, such as

Il

CH, = CHNC

CH, = CHCH ₅ NC

₂ = CHCH ₂

CH ₂ = CH (CHj) ₂ NC
CH-CH, O

I ^ ι

0 CHNC

Il /

CH-CH ₂

CH ₂ = CHCH ₂

Polyisocyanates, which in combination with olefinic

unsaturated monohydroxy compounds of the form

(7) may have been used to create terminal olefinic unsaturation in the copolymer are for example

CH,

// V

Il

NC

or

Il

NC

40 CN

Il

Silicon-hydrogen-containing compounds of the formula (4) are, for example, acyloxysilane of the formula

R ₀ O

HSi (OCV) ₃ _ _a
in which V is hydrogen or an alkyl radical, e.g. R.

Il

HSi (CHa) ₂ (OCCH ₃ )

Il

HSi (OCC ₂ H ₅ J ₃
O

Il

HSiCH ₃ (OCC ₂ H ₅ J ₂ O

• Il

HSi (OCCHj) ₃ O

HSiCH ₃ (OCH) ₂

Keloximatosilanes, like

HSiCH ₃ [ONC (CH ₃ ) (C ₂ H ₅ O ₂ HSi (CH ₃ J ₂ [ONC (CH ₃ ) (C ₂ H ₅ )]

HSi [ONC (CH ₃ ) (C ₂ H _s )] ₃ or

HSiCH ₃ [ONC (CH ₃ ) J ₂

■ or halosilanes, such as

HSiCl ₃ (CH ₃ J ₂ HSiCl CH ₃ HSiF ₂ CH ₃ HSiCl ₂

The bisphenols of the formula (9) include:

2,2-bis (4-hydroxyphenyl) propane

(Bisphenol-A),

2,4'-dihydroxydiphenylmethane,

Bis (2-hydroxyphenyl) methane,

Bis (4-hydroxyphenyl) methane,

1,1 bis (4-hydroxyphenyl) ethane,

l, 2-bis (4-hydroxyphenyl) ethane,

1,1 bis (4-hydroxy-2-chlorophenyl) ethane,

1,1 bis (2,5-dimethyl-4-hydroxyphenyl) -

ethane,

13-bis (3-methyl-4-hydroxyphenyl) propane,

2,2-bis (3-isopropyl-4-hydroxyphenyl) propane,

2,2-bis (4-hydroxyphenyl) -hexylfluoropropane ₎

4,4'-sec -butylidenediphenol,

4,4'-methylene (2,6-di-tert-butylphenol) or

2,2'-methylene (4-methyl-6-tert-butylphenol).

In addition to the bisphenols of the formula (9), further examples of dihydroxy compounds of the formula (3) are from the book by Herman Schnell quoted above, Chemistry and Physics of Polycarbonates. Other examples of usable dihydroxy compounds shows the table on pages 162 to 163 of the book Polycarbonates by William F. Christop h e r and Daniel W. F o χ, Rheinhold Publishing Corp. (1962). Such dihydroxy compounds are represented by, for example, the following formula

CH ₃ HSiBr ₂

Alcohols encompassed by the formula (7) are aliphatically unsaturated alcohols such as

CH ₂ = CH - CH ₂ OH

OH

CH ₃ - CH = CH - CH ₂ OH linalool (SJ-dimethyl-lo-octadien-S-ol)

OCH ₂ CH = CH ₂

OH

CH ₂ = CH - CH - CH ₂ CH ₃ OH

CH ₂ -CH = CH ₂

CH ₂ = CH - CH ₂ - CH ₂ CH ₂ OH

OH

CH ₂ -CH = CH ₂

^ho O ^q O ^oh

or

CHsC-CH ₂ OH

includes, in which Q, for example, 1,1-cyclopentyl
- O - - OC ₆ H ₅ O - - S -

O O

I Il

- s— —s -

Il ο

R "

- Si -

R "

can be.

The organopolysfloxane-polycarbonate block copolymers which contain organosilyl radicals of the formula (1) linked via carbon-silicon bonds in rubber-like products with elongations at break of up to 1000% or more or in practically hard masses transferable that have an elongation of less than 200%. The elongation depends on the weight of the organopolysubxane blocks, based on the Total weight of the organopoly doxan and polycarbonate

6s nat copolymers. By using copolymers with 50 to 95 percent by weight, preferably 50 up to 85 percent by weight OrganopotysQoxane, based on on the total weight of the copolymer, can

Organopolysiloxane elastomers with valuable properties can be produced. Under the use of less than 50 weight percent organopolysiloxane based on the weight of the copolymer will be practically hard film-forming compositions produced which are advantageously used for coating purposes can.

The room temperature curable copolymers can be used for many conventional applications are needed for which organopolysiloxane elastomers and polycarbonates are suitable. Special types of application are roof coverings, coatings for aluminum strands, elastomers with improved solvent resistance, flexible windows for vehicles, transparent rubber seals for glass windows, insulating material, solid or rubber-like clear coatings for construction purposes on wood or copper.

In the practice of the invention, the addition of silicon-hydrogen is carried out containing compound of the formula (4) to the organopolysiloxane polycarbonate BIock copolymers having the aliphatic unsaturation at a temperature in the range from 20 ⁰ C to 200 ⁰ C. The addition preferably takes place in the presence of a platinum catalyst, for example a platinum-olefin complex compound, as described in US Pat. No. 3,159,601, or a chloroplatinic acid alcoholate. as described in US Pat. No. 3,220,972 instead. The aliphatically unsaturated copolymer is produced by the action of phosgene on a mixture of a dihydroxy compound of the formula (3), an organopolysiloxane of the formula (6) and an aliphatically unsaturated monohydroxy compound of the formula (7) at a temperature of 0 ° C to 200 ° C

The ordinary temperature curable copolymers are preferably used in conjunction with a suitable organic solvent in order to facilitate the application of the copolymer to the substrate. Suitable organic solvents are e.g. B. methylene chloride, benzene, tetrahydrofuran, chloroform, dioxane or sym-tetrachloroethane. The copolymers curable at ordinary temperature in combination with suitable solvents can further be used in combination with fillers, up to 100 parts of filler per 100 parts of copolymers being used. Suitable fillers are carbon black, diatomaceous earth, silicon dioxide obtained from flue gas, titanium dioxide and iron oxide.

It has been found that the compositions containing the curable copolymers with other constituents, such as solvents and fillers, ^{can remain stable for at least 6 months or longer at temperatures from 0 °} C. to 100 ^° C. if they contain no more than 100 parts of water per million Teüe of molding compound are included. Known methods can be used to reduce the presence of water in the molding compositions. In addition, the components can be mixed under moderate conditions, for example a nitrogen atmosphere.

Finally, the curable at room temperature molding compositions can except mn the abovementioned components such as solvents and fillers, with Härtebeschleunigem as lead octoate, stannous Dibutyürinndilaurat or be mixed.

The following examples illustrate the invention. AHe TeHe are parts by weight.

example 1

A chlorine-endblocked polydimethylsiloxane clv " average formula

I I I

Cl-i-SiO 4-SiCl

I ι ι

! CH, _M CH.,

ι? was prepared by; nan within, Stunu> .. i a mixture of 100 parts What ... and 200 parts of dioxane to 800Teilen Dimcthyldic · !, iJ ..?! '^ l ⁿ mixture was stirred and so eye! ur.icr gently refluxed until it became homogeneous.

Thereafter, the volatile constituents were vacuumed up to an internal temperature of 200 "C at 12 nm Pressure removed. The hydrolyzable chlorine content was 4.6%.

A solution of 225 parts of the above chlorine-terminated bitumen was used Polydimethylsiloxane in 130 parts of dry methylene chloride became a mixture of 114 parts 2,2-bis (4-hydroxyphenyl) propane, 1300 parts of methylene chloride and 130 parts of dry pyridine were added. The addition took place within 65 minutes.

while the resulting mixture was vigorously stirred. After the method of manufacture was a Polydimethylslloxane obtained, the terminal radicals of the formula

CH,

owned.

Phosgene was introduced into the mixture, which consisted of the above polydimethylsiloxane and 2,2-bis (4-hydroxyphenyl) propane, within 50 minutes at a rate of 0.74 parts per minute. During the phosgene treatment, the temperature rose 38 ° C. The introduction of phosgene was continued until phosgene was found in the exhaust gases . The mixture was then purged with nitrogen. An aqueous solution of pyridine was added. The copolymer was precipitated by adding methanol to the mixture. The copolymer was then washed four times with added methanol. After drying at 100 ^° C., a copolymer was obtained which has the terminal radicals of the formula

owned. The intrinsic viscosity in chloroform was 0.23 dl / g. According to the method of manufacture that was Copolymers of 36 percent by weight of polycarbonate blocks, with 64 percent by weight of polydimethylsfl-

oxane blocks of the average formula

CH,
SiO-

CH,

linked based on the weight of the copolymer

1.83 parts of allyl isocyanate were added to a solution of 50 parts of the above-described copolymer in 250 parts of dry toluene in the presence of 0.02 part of dibutyl tin flaurate. ^{The mixture was heated to 100 °} C. for 22 hours under practically anhydrous conditions and a further 0.02 part of dibutyltin dilaurate was added. After refluxing for 24 hours using 0.06 parts of zirconium octoate, infrared analysis indicated that the mixture was free of isocyanate. According to the method of preparation, the copolymer obtained had terminal radicals of the formula

Il

OCNHCHjCH = CH ₂

To the mixture, 0.0028 parts of platinum in the form given to a chlorine Platt acid-octyl alcohol complex compound, and the solution was heated to 90 ⁰ C. For this purpose, 3.57 parts of methyldiacetoxysilane were added. After heating at 100 ° C. for 11 hours, the infrared analysis showed that the addition of the silicon hydride-containing compound to the allylene endblocked polymer was completed. Following the process of preparation a copolymer was obtained which has terminal radicals of the formula

CR,

CH ₃

OCNHCH ₂ CH ₂ CH ₂ SiI OCCH ₃ ) ₂ then added a solution of 2 parts of water in 5 parts of pyridine. The product was precipitated by adding methanol. Additional methanol was washed three times in a mixer. By the method of manufacture, the product was a copolymer composed of 64 weight percent polydimethylsiloxane blocks linked to 36 weight percent polycarbonate blocks based on the weight of the copolymer. It had terminal groups of the formula

Il

-OCOCH ₂ CH = CH ₂

which were bonded with polycarbonate blocks.

The above procedure was repeated except that the allyl alcohol was replaced initially 2.75 parts of 2-allylphenol and at the end of the phosgenation 5 parts of 2-allylphenol were added. It was a copolymer with radicals of the formula

-OCO

CH ₅ CH = CH ₂

owned. This molding compound was poured into an aluminum tray. A non-adhesive sheet was obtained when the mixture was kept under atmospheric conditions for 2 hours. After 48 hours, the tensile strength of a sample of the cured copolymer was 28 kg / cm ² at 200% elongation. These results were a remarkable improvement over uncured copolymer.

Example 2

With stirring, 225 parts of the chlorine-endblocked dimethylsiloxane des were within 70 minutes Example 1 in 130 parts of methylene chloride to a mixture of 114 parts of 2,2-bis (4-hydroxyphenyl) propane and 130 parts of dry pyridine and 1300 parts Given methylene chloride. Thereafter, 1.3 parts of allyl alcohol was added to the mixture. Well it became like that long phosgene introduced into the mixture until the presence of phosgene in the exhaust gases Indicated completion of implementation. Then nitrogen was bubbled into the mixture for 15 minutes, to drive off the excess phosgene. Then 5 parts of allyl alcohol and obtained connected with polycarbonate blocks.

The above-described allyl endblocked copolymer (A) and the allylphenyl endblocked copolymer (B) were then treated at ordinary temperature by the following procedure

A mixture of 50 parts allylcarbonatendblokkiertem copolymer (A), 220 parts of toluene and 0.0028 part of platinum in the form of a platinum alcoholates, as used in Example 1 was heated to 90 ⁰ C. Thereafter, partly within 7 days 7, 6 parts of methyldiacetoxysilane were added to the solution. The addition was carried out under practically anhydrous conditions. After the addition was complete, 5 parts of the solution and 0.02 part of stannous octoate were placed in a small aluminum dish and the molding composition according to the invention was exposed to atmospheric conditions. After 2 hours one was non-sticky

Foil has been formed. After 24 hours, a sample was cut out of the film.

The above procedure was repeated with the modification that 2-allylphenyl carbonate end-blocked copolymer (B) was used in place of (A). The methyldiacetoxysilane was added in 2 hours. Part of the solution was poured onto a small aluminum dish with the addition of 0.004 part of dibutyltin dilaurate and the molding composition according to the invention was exposed to atmospheric conditions. The film was tack-free after 2 hours. A sample was cut from the film. The following table shows the results obtained with the copolymer (A) and the copolymer (B) in terms of “T” tensile strength and “E” elongation (percent) before and after curing.

Unhardened
Γ kg / cm * E

Hardened T kg / cm ²

A. 13th 175 62.6 330 B. 20.7 250 58.0 175

Example 3

; A mixture of 1480 parts and 260 parts ÖCtamethylcyclotetjrasiloxam ^ -Diaiethyl-l-oxa ^ -silacyciöhexan and 26l) share _{2J-Diniethyl-1-oxa-2-silacycIohexan} was 2 hours in the presence of 1.8 parts kaDuinhydroxyd at 180 ⁰ C equilibrated. The product obtained was clear and homogeneous. After the product had cooled to below 40 ° C., it was hydrolyzed with acetic acid. The oil obtained was then neutralized and dried with anhydrous soda and filtered through diatomaceous earth. This process gave a hyiiiroxybutyldimethylsiloxy-endblocked polydimethylsiloxane which contained an average of 20 chemically linked dimethyliloxy units. '

A mixture of 800 parts of the above polydimethylsiloxane hydroxybutyldiriiethylsiloxyenclblockierten, 5 (i2 OcUimethylcyclotetrasiloxan parts, 34.4 parts of 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 13 parts of potassium hydroxide were added 2.5 stun the stirred at 180 ⁰ C for After the mixture to room temperature Once cooled, it was mixed with 6 parts of concentrated hydrochloric acid. The mixture was then stirred for 1 hour, 20 parts of sodium bicarbonate being slowly added. The mixture was then filtered and the filtrate ^{removed in vacuo at 180 °} C. and 4 torr hydroxybutyldimethylsiloxy-endblocked polydiorganosiloxari with an average of 40 chemically linked diiorganosiloxy units, which essentially comprised dimethylsiloxy units and 2.5 mol percent of methylvinylsiloxy units, based on the total amount of diorganosiloxy units.

The block copolymers with terminal groups of the formula

Il

CH ₂ == CHCH ₂ OCO -

was by introducing phosgene into a mixture of 57 parts of 2,2-bis (4 hydroxyphenyl) propane, 1340 parts of methylene chloride, 75 parts of pyridine, 13 parts, len allyl alcohol and 75 parts of the hydroxybutyldimethylsiloxy endblocked polydiorganosiloxane described above manufactured. The obtained copolymer was made by precipitation with methanol, washing, etc., such as It was obtained in 90% yield, based on the starting materials. According to the method of manufacture, the copolymer consisted of 54 weight percent polydiorganosiloxane blocks, which Terminal units of the formula

CH,

- OSiC ₄ H ₈ O CH ₃

possessed which were chemically linked with 46 weight percent polycarbonate blocks, based on the weight of the copolymera. It had a tensile strength wedge of 35.7 kg / cm ² and an elongation of 50%.

To a mixture of 50 parts of the above block copolymer, 0.0014 parts of platinum in the form of the complex compound of Example 1 was applied, and 240 parts of benzene were within 12 minutes 2.3 parts of methyldiacetoxysilane in benzene Solution given. The mixture was refluxed for 2.5 hours according to the procedure The preparation gave a copolymer curable at room temperature, the terminal residues the formula

O CH ₃

- OCOC ₃ H ,, Si (OCCH ₃ ) ₂

owned. A portion of the copolymer solution containing 0.25 percent by weight dibutyl zirine dilaurate was poured into an aluminum dish. A non-adhesive film was obtained from the molding composition according to the invention in less than 2 storms. A cured test strip showed a tensile strength of 125 kg / cm ² and an elongation at break of 85%.

Example 4

An organopolysiloxane-polycarbonate copolymer with terminal groups of the formula

Il

CH ₂ = CHCH ₂ OCO-

was according to the method of Example 3 by passing phosgene into a mixture of 114 parts of 2,2-bis (4-hydroxyphenyl) propane, 45 parts of hydroxybutyldimethylsiloxy-endblocked polydiorganosiloxane of Example 3, which contained 40 chemically linked diorganosiloxy units, 0.86 parts of allyl alcohol, 2700 parts of methylene chloride and 140 parts of pyridine the phosgene was carried out within 160 minutes at a temperature of 26 ° C to 33 ⁰ C. in the process of manufacture was the copolymer obtained from 27 percent by weight Polydiorganosiloxanblöcken, the terminal units of the formula

CH,

- OSiC ₄ H ₈ O
CH ₃

possessed and 73 weight percent chemically linked polycarbonate blocks based on the weight of the Copolymers

An organopolysiloxane-polycarbonate copolymer curable at ordinary temperature with terminal

O CH ₃

Il I

- OCOCASHOCCH ^ residues

55 was prepared by adding 33 parts of methyldiacetoxysilane in tetrahydrofuran to a mixture of 50 parts of the above organopolysiloxane-polycarbonate block copolymer, 240 parts of tetrahydrofuran and 0.0014 part of platinum, which was used in the form of the catalyst used in Example 1.

A sample of the mixture was poured into an aluminum pan. A catalytic amount of stannous octoate was admitted. In addition, 3 parts of methyltriacetoxysilane was added to the mixture. One in Cured film insoluble in methylene chloride was obtained from the molding composition according to the invention.

Example 5

A mixture of 200 parts of the polydiorganosiloxane of Example 3, the average of 40 chemically linked Diorganosüoxvemheiten and terminal hydroxybutyl-dimethylsiloxy units contained,

21.5 parts of toluene diisocyanate and 1100 parts of chlorobenzene were heated to ltJb ° C for 4 hours. The mixture obtained was stirred into a solution of 114 parts of 2- bis (4-hydroxyphenyl) propane, 130 parts of dry pyridine and 1100 parts of chlorobenzene poured. 13 parts of allyl alcohol were added. Phosgene was introduced into the mixture. At the end of the phosgene introduction, which was determined by the presence of the phosgene in the exhaust gases, a further 8.6 parts of allyl alcohol were added to the mixture to remove excess phosgene and chlorocarbonate end groups. The copolymer was then precipitated with methanol and, after washing with methanol, ^{dried in a drying cabinet at 100 °} C. According to the method of production, the copolymer contained terminal radicals of the formula

Il

CH ₂ = CHCH ₂ OCO -

It contained 64 percent by weight of terminal polydiorganosiloxane blocks

CH ₃ O

- OSiC ₄ H ₈ OCNH / ~ \ cH ₃ units

CH,

NH
O = CO-

linked with 36 weight percent polycarbonate blocks, based on the weight of the copolymer !! was.

To a mixture of 50 parts of the above copolymer and 240 parts of benzene, in Presence of 0.0014 parts of platinum in the form of the catalyst used in Example 1, 2.3 parts Given methyldiacetoxysilane. The molding compound is then heated for 2 hours and then part of it poured into an aluminum tray and allowed to harden under atmospheric conditions. there has been a tough film obtained which was insoluble in methylene chloride.

Example 6

A mixture of 50MoI octamethylcyclotetrasiloxane per mole of tetramethyl-1,3-bis (}> - carboxypropyl) -disiloxane was using 3 percent by weight of an 86% sulfuric acid for 2 hours 100 ° C equilibrated The mixture was cooled and the liquid organopolysiloxane from the acid in one Separating funnels separated The liquid organopolysiloxane was washed with water and over sodium sulfate dried. According to the method of manufacture, the liquid was a carboxy-endblocked polydimethylsiloxane the average formula

H OCH ₆ C ₃ -

CH ₃

SiO

CH,

'3,000

CH ₃ O

I Il

SiC ₃ H ₆ COH
CH ₃

45

The above organopolysiloxane was then absent heated by atmospheric moisture with thionyl chloride, which is used in such an amount which is sufficient to convert the above polydimethylsiloxane into a terminal polydimethylsiloxane

CH ₃ O

CH ₃

to convert. A sufficient amount of calcium carbonate was also used to reduce the

to neutralize the hydrogen chloride formed and to absorb. The mixture was for 3 hours Then pyridine was added dropwise until no more pyridine hydrochloride was formed. then a small amount of carbon black was added to the mixture. The mixture was then filtered and under kept practically anhydrous conditions.

200 parts of the above poly-dimethylsiloxane with terminal units of the formula

CH ₁ O

- OSiC ₃ H ₁₁ CCl

CH ₃

were within 30 minutes to a stirred solution of 114 parts of 2,2-bis (4-hydroxy phenyl) propane, 130 parts of dry pyridine and 3300 parts of methylene chloride were added. To the mixture obtained 1.3 parts of allyl alcohol were then added. In order to effect the copolymerization, the Phosgene mixture passed in. Excess phosgene and chlorocarbonate end groups were added by adding destroyed by allyl alcohol. The mixture was then converted into 287 parts of process product by adding methanol failed. In terms of the method of manufacture, the product was a copolymer with terminal

CH ₂ = CHCH ₂ OCO radicals

associated with polycarbonate blocks; it contained 61 percent by weight polyorganosiloxane, made of Terminal polydimethylsiloxane blocks

CH ₃ O

55 CH ₃

and 39 weight percent chemically linked polycarbonate blocks based on the weight of the Copolymers.

To 50 parts of the above copolymer, i.e. ice dissolved in 240 parts of boiling benzene, were added 0.0014 parts of platinum in the form of the catalyst compound used in Example 1 and 2.5 parts of methyldiacetoxysilane given. The mixture was heated for 2 hours. The product obtained was with a catalytic amount of dibutyltin dilaurate treated after exposure to atmospheric moisture

cured the 'molding composition according to the invention to form an insoluble film.

Example Γ

Following the procedure of Example 6, a mixture of 2MoI Octamethylcyclotetrasiloxan pro Moles of tetramethyl-t3-bis (γ-carboxypropyl) -disiloxane Equilibrated a polydimethylsiloxane of the average formula

O CH ₃

Il I

HOCC ₃ H ₆ Si-CH,

CH,
OSiO

CH ₃

CH ₃ O

I Il

-SiC ₃ H ₆ COH
CH,

obtain. The polydimethylsiloxane is then treated with thionyl chloride according to the procedure of Example 6 treated to a polydimethylsiloxane terminated with

CH ₃ O

I Il

CH ₃
to manufacture.

A solution of 100 parts of the above polydimethylsiloxane in methylene chloride is then prepared within 30 up to 45 minutes to a mixture of 57 parts of 2 ^ -Bis- (4-hydroxyphenyl) propane, 1300 parts of methylene chloride and 65 parts of pyridine. 0.65 parts of allyl alcohol are added. With vigorous stirring Phosgene is added to the mixture at a rate of 0.5-0.06 parts per minute for 2 hours The phosgene feed is interrupted when unconverted phosgene appears in the exhaust gases A further 10 parts of allyl alcohol are then added to the mixture. The process product becomes then precipitated according to the method described above and dried according to the method of To make the product was a copolymer terminated with allyl carbonate blocks with the polycarbonate were linked. The copolymer consisted of 58 weight percent polydimethylsiloxy blocks with terminal

T ' ?

- OSiQHeCO units
CH ₃

linked to 42 weight percent polycarbonate blocks based on the weight of the copolymer was.

A solution of 50 parts of the above copolymer and 270 parts of boiling benzene was 0.015 parts Mixed platinum in the form of a chloroplatinic acid-octyl alcohol complex compound was applied. To the mixture obtained was added 2.5 parts of methyldiacetoxysilane given. The mixture was heated for 2 hours. After cooling to room temperature a catalytic amount of stannous octoate was added to the mixture. Some of the solvent-based, Molding composition according to the invention was placed in a tin-plated steel shell and under atmospheric conditions exposed. A film was obtained after 16 hours. It was insoluble in methylene chloride.

Example 8
At 90 ° C 294 parts of a Polydimethyisil-

oxans the average formula

CH ₃
SiO

CH ₃

H- ^L SiO

CH ₃

SiH

CH ₃

to a mixture of 60 parts of 2-Aylphenol and 0.0014 part of platinum, which was used as the chloroplatinic acid alcoholate complex compound. The mixture was stirred for 3 hours at a temperature of 90 ³ C to 115 "C. An infrared spectrum of a portion of the mixture showed that it was free of silicon hydride. The mixture was cooled to room temperature. The product: was obtained by extraction with Methylene chloride and subsequent washing of the extract with a solution of 4 parts of methanol per part of water. The product is dried with anhydrous sodium sulfate and the solvent is removed in vacuo up to a temperature of 115 ° C. According to the method of preparation was the product is a polydimethylsiloxane of the average formula

OH

CH,
SiO

CH,

SiC ₁ H ,, <
! CH ₃ L ₀ CH ₃ OH

Phosgene was in a mixture of 57 parts of 2,2-bis (4-hydroxyphenyl) propane, 70 parts of pyridine, 1300 parts of methylene chloride, 100 parts of the above polydimethylsiloxane with terminal y- (2-hydroxyphenyO-propyldimethylsiloxy units and 2.95 parts of 2-allylohenol. The mixture was so long treated with phosgene until unreacted phosgene was contained in the exhaust gases. An excess Amount of 2-allyl phenol was then added to the mixture given to bind the excess phosgene or the chlorocarbonate end groups. The copolymer was then precipitated by adding methanol according to the procedures described above. It 150 parts of copolymer were obtained, the terminal radical of the formula

Il o — c — o—

CH ₂ = CHCH ₂ V

owned. The yield was 88%, based on the 'starting materials. The copolymer contained polydimethylsiloxane blocks with terminal

CH ₃ O
-OSiC ₃ H ₆ / S units

CH ₃
which were linked with polycarbonate blocks.

50 parts of the above copolymer was dissolved in 240 parts of dry benzene. To this solution, 0.0014 part of platinum in the form of a platinum alcoholate complex compound was added and the resulting mixture was refluxed. Then 2.3 parts of methyldiacetoxysilane were added over the course of 6 minutes. The mixture was refluxed for 45 minutes. Then 0.14 part of dibutyl tin dilaurate was added to 35 parts of the mixture. The molding composition according to the invention was then exposed to atmospheric conditions in a tin-plated shell. It was tack free after 3 hours. A crosslinked, insoluble film was obtained after 40 hours. The test strips were pulled through a tensile tester at a crosshead speed of 5 cm / min. The test strips had a tensile strength wedge of 105 kg / cm ² and an elongation at break of 125%.

Example 9

There were 225 parts of the chlorine-endblocked polydimethylsiloxane from Example 1 in 130 parts of methylene chloride to a mixture of 76.5 parts of bis (4-hydroxy-2,5-dimethylphenyl) sulfone, 130 parts of pyridine and 1300 parts of methylene chloride within 50 minutes given. A mixture of 57 parts of 2,2-bis (4-hydroxyphenyl) propane and 1.3 parts of allyl alcohol was then added filled. Phosgene was then introduced into the mixture until unreacted phosgene entered the Exhaust gases was detected. Thereafter, an additional 8.5 parts of allyl alcohol was added to the mixture. By Adding methanol to the mixture, according to the procedure previously described, becomes the copolymer precipitated, the terminal one

35 O

Ii

CH ₂ - = CHCH ₂ OCO - radicals

possesses linked to polycarbonate blocks. According to the method of manufacture, the copolymer contains 61 percent by weight organopolysiloxane, which consists of polydimethylsiloxane blocks, which with 39 weight percent polycarbonate blocks by bonds, how

O
CH ₃ CH ₃ I CH ₃

CH ₃ CH ₃ CH ₃

55

O -

are linked. A film is cast from the methylene chloride solution of the copolymer, it shows valuable elastic and insulating properties

There are 23 parts of methyldiacetoxysilane to one Solution of 50 parts of the above copolymer in 270 parts of dry benzene and 0.0014 parts of platinum in Form a platinum alcoholate complex compound while the solution is refluxed.

The mixture is then heated for 3.5 hours. Thereafter, a catalytic amount of dibutyltin dilaurate becomes the Mixture given: the molding compound according to the invention is then poured into an aluminum tray. To A non-adhesive sheet was obtained for 2.5 hours after exposure to atmospheric conditions for 24 hours Conditions a product insoluble in methylene chloride is obtained.

Example 10

55.5 parts of water are added dropwise over the course of 2 hours to a solution of 400 parts Dimethyldichlorosilane given in 290 parts of diethyl ether. The mixture continued with stirring Heated under reflux for 1.5 hours. After removal of the solvent, a product was obtained which Contained 1.56% hydrolyzable chlorine. Following the method of manufacture was a chlorine endblocked Polydimethyisiloxane obtained containing an average of 60 chemically linked dimethylsiloxy units

A solution of 600 parts of the above polydimethylsiloxane in 134 parts of methylene chloride was added with stirring to a mixture of 114 parts of 2,2-bis (4-hydroxyphenyl) propane, 130 parts of pyridine and 2700 parts of methylene chloride over the course of one hour. Thereafter, 1.5 parts of allyl alcohol was added to the mixture. Phosgene was then bubbled into the mixture for 4 hours. The mixture was finally flushed with nitrogen to remove excess phosgene. Then 8.6 parts of allyl alcohol were added, which reacts with the chlorocarbonate end groups. By addition of methanol a product was precipitated, which ausmachie 612 parts by washing four times with methanol and dried at 100 ⁰ C. According to the method of preparation, the product was an unsaturated copolymer terminated with allyl carbonate groups consisting of 83 weight percent organopolysiloxane consisting of polydimethylsiloxane blocks with 17 weight percent polycarbonate blocks based on the weight of the copolymer. were combined.

To 50 parts of the above copolymer in 270 parts of benzene was added 23 parts of methyldiacetoxysilane. Then 0.0014 parts of platinum in the form of the catalyst used in Example 7 were added. The mixture was refluxed for 20 minutes and then 0.14 part of dibutyltin dilaurate was added. The molding composition according to the invention was allowed to harden under atmospheric conditions. It was tack free after 2 hours. It showed a tensile strength of 23 kg / cm ² and an elongation of 340%.

Example 11

A solution of 52 parts water in 79 parts acetone was added to 400 parts dimethyldichlorosilane within 2 hours. The Ge obtained was mixed heated for 13 hours at a temperature voi 51 ⁰ C and then evaporated at reduced pressure di volatiles to give 187 part of a chlorendblockierten liquid received dl · 2.44 weight percent hydrolyzable chlorine be seated Based on the method of production is the resulting chlorine-endblocked polydimethylsil

609530/41

oxane from 39 'chemically linked dimethylsiloxy units built up.

A solution of 23 parts of the above-mentioned polydimethylsiloxane in 70 parts of methylene chloride was added dropwise with stirring to a mixture of 114 parts of 2,2-bis (4-hydroxyphenylj-propane, 1340 parts of methylene chloride and 130 parts of pyridine) over 20 minutes 0.86 parts of allyl alcohol was added and then phosgene was bubbled into the stirring mixture for 2.5 hours and then a further 7.5 x parts of allyl alcohol were added, following the procedure of Example 10. 130 parts of reaction product was obtained This product is a copolymer consisting of 15 percent by weight organopolysiloxane, which in turn is composed of polydimethylsiloxane blocks, and 85 percent by weight of polycarbonate blocks chemically linked to it, the percentages by weight referring to the weight of the copolymers.

2.3 parts of methyldiacetoxysilane were added to a solution of 50 parts of the aforementioned copolymer added in 220 parts of benzene. Then 0.0014 parts of platinum catalyst, which is also in the Example 9 used was added. The reaction mixture was refluxed for 20 minutes conditions kept at the boil and 0.88 part «dibutyltin dilaurate added. If you have this if the molding compound according to the invention is applied to a tin plate and exposed to moisture, a solid « Foil.

The curable at ordinary temperature, invent molding compositions according to the invention can be converted into one

ίο A large number of technically valuable products are processed, such as films or elastomers, which can lead to the application methods for polycarbonate and organopolysiloxane trains that are well known in the art.

An outstanding feature of the molding compositions according to the invention is that the cured form masses a sudden increase in strength compared to the non-hardened, thermoplastic, in dei Have copolymers containing molding compounds.

The molding compositions curable at ordinary temperature can also advantageously be in the form of their solution in an organic solvent and in organic solvents! be made insoluble after curing with moisture.

Claims (4)

Patent claims: 1. With a content of S 100ppm water storable molding or sealing compound based on block copolymers, which have C-Si bonds monovalent organosilyl radicals of the formula where Y is a hydrolyzable radical, R is one of aliphatically unsaturated bonds free monovalent hydrocarbon radical or a halogenated one monovalent hydrocarbon radical and a is a value of 0.1 or 2, contain bonded, which hardens on contact with atmospheric moisture and which, in addition to fillers, optionally Solvent, also containing catalyst, characterized in that the copolymers from chemically linked »blocks of (A) 1 to 95 percent by weight organopolysiloxane, which in turn consists of chemically linked diorganosiloxy units the formula R ^ SiO is constructed, as well (B) 5 to 99 percent by weight of a reaction product from the conversion of a dihydroxy compound the formula HO-Z-OH with a dihalide of carbonic acid or a diaryl carbonate, where R 'is a monovalent one Hydrocarbon radical, a halogenated monovalent hydrocarbon radical or a cyanoalkyl radical and Z is the same as R "or R" WR ", where again R" is a divalent one Hydrocarbon radical or a halogenated divalent hydrocarbon radical and W is a divalent R '"
- C - rest R '" a divalent cycloaliphatic radical, a divalent oxyarylenoxy radical, a sulfonyl, Sulfinyl, oxy or thio radical and R '"denotes hydrogen or an R radical 2. Molding composition according to claim 1, characterized in that the organosilyl radicals by divalent organic residues of the formula in turn from 1 to 500 chemically linked diorganosiloxy units of the formula R ' --SiO-- R ' is built up, and from (B) 5 to 99 percent by weight of the reaction product of a dihydroxy compound of the formula HO OH with a dihalide of carbonic acid, where the symbol Q denotes the following groupings means: Il - o— —co - - OCO - - NHCO -
OO Il Il - OCNHR'NCO OO O Il Il Il OCR'TO - - COR'O - Il - SC (R '") ₂ CO - furthermore R, R ', R "and R'" have the meaning given in claim 1, E is halogen or an alkyl radical, ζ O, 1 or 2, d 0 or 1, the grouping R '" CRi "C (H) part of a saturated aliphatic or cycloaliphatic radical and / 0 or a whole Means a number from 1 to 4 inclusive 3. Molding composition according to claim 2, characterized in that the polyorganosiloxane blocks of the Copolymers through R '"
CRi "QH) R" Q R ¹ -SiO
R ' R " O bonds to the copolymer via carbon-silicon bonds are bound and that the copolymer of chemically linked blocks from (A) 1 to 95 percent by weight of polydiorganos uoxyn linked to the polycarbonate blocks, with the symbols R 'and R' "those specified in claim 1 and the symbols E and / that specified in claim 2 Have meaning. 4. molding compound according to claim 1 or 2, characterized characterized in that the polycarbonate blocks are chemically linked with polyorganosiloxane blocks, which last terminal R ' . I. - OSiR'O units